Role of entropy in supramolecular photochirogenesis: enantiodifferentiating photoisomerization of cyclooctenes in chiral sensitizer-immobilized MCM-41 cavities
Role of entropy in supramolecular photochirogenesis: enantiodifferentiating photoisomerization of cyclooctenes in chiral sensitizer-immobilized MCM-41 cavities
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DOI：
10.1039/c1pp05087g
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发表时间：
2011-01-01
影响因子：
3.1
通讯作者：
Inoue, Yoshihisa
中科院分区：
文献类型：
--
作者：
Maeda, Ryo;Wada, Takehiko;Inoue, Yoshihisa
为了研究限制或低熵环境的影响，我们采用了介孔硅酸盐MCM-41修饰的光学活性苯四甲酸酯作为手性反应介质，影响（Z）-环辛烯和（Z，Z）-1，5-环辛烯的对映异构化。在MCM-41中生成的（E）-异构体的ee值及其温度依赖性行为与在均相溶液中观察到的完全不同。将敏化剂固定在MCM-41中，降低了熵因子的贡献。
To examine the effects of confinement, or low-entropy environments, we employed the mesoporous silicate MCM-41 modified with optically active benzenetetracarboxylates as chiral reaction media to effect the enantiodifferentiating photoisomerization of (Z)-cyclooctene and (Z, Z)-1,5-cyclooctadiene. The ee of the (E)-isomer produced and its temperature dependence behavior in MCM-41 were completely different from those observed in homogeneous solutions. Immobilizing the sensitizer in MCM-41 reduced the contribution of the entropy factor.